A kind of method of synthesizing diphenyl alkane compound

Abstract

The invention discloses a method for synthesizing diphenyl polynitro compounds, and belongs to the field of organic synthesis. The method is realized through the following steps that under the water-free and oxygen-free conditions, methylbenzene is used as a starting raw material to take a reaction with n-butyllithium under the condition of using tetrahydrofuran as an activating agent; then, obtained materials take a reaction with alkane dichloride to obtain the diphenyl polynitro compounds. The method has the advantages that the reaction conditions are mild; the yield is high; the operation is easy; the production cost is reduced; the industrialized production is easy.

Description

technical field

[0001] The invention relates to a synthesis method of a class of organic compounds, in particular to a synthesis method of diphenylalkane, and belongs to the field of organic synthesis. Background technique

[0002] As a class of important intermediates, diphenylalkane compounds play an important role in the field of fluorescent probes. In addition, they can also be used as precursors for the synthesis of calixarenes and initiators for polymerization reactions. Diphenylalkane compounds also have a significant effect in improving the viscosity index of lubricating oils.

[0003] At present, the synthesis methods of diphenylalkane compounds mainly include: (1) the coupling of aryl Grignard reagent and dihaloalkane under metal complex catalysis to obtain diphenylalkane compound (Chem. Eur. J. 2009, 15, 3889; Chem. Commun. 2006, 4726; Tetrahedron 2006, 62, 2207); (2) Aromatics and ClO(CH 2 ) n COCl undergoes Friedel-Crafts reaction under the action of aluminum...

Examples

example 1

[0013] Example 1 Synthesis of 1,3-diphenylpropane

[0014] Under argon protection, 10 mL of toluene was added to the dry reaction vessel at 20 °C, then 8 mL of n-butyllithium (2.5 M n-hexane solution) was added dropwise with stirring, and 10 mL of tetrahydrofuran was slowly added dropwise at the end of the addition. After reacting at 20 ºC for 3 hours, add 0.85 g of dichloromethane dropwise to the reaction system, and react for 3 hours after dropping, add water to quench the reaction, then separate the layers, dry the organic layer with anhydrous magnesium sulfate, filter and distill under reduced pressure to obtain 1,3-diphenylpropane 1.24g, yield 63%. 1 HNMR (400MHz, CDCl 3 ) δ = 1.96-2.06 (m, 2H), 2.66-2.74 (m, 4H), 7.19-7.25 (m, 6H), 7.27-7.35 (m, 4H).

example 2

[0015] Example 2 Synthesis of 1,4-diphenylbutane

[0016] Under argon protection, 10 mL of toluene was added to the dry reaction vessel at 20 °C, then 8 mL of n-butyllithium (2.5 M n-hexane solution) was added dropwise with stirring, and 10 mL of tetrahydrofuran was slowly added dropwise at the end of the addition. After reacting at 20 ºC for 3 hours, add 1.0 g of 1,2-dichloroethane dropwise to the reaction system, and react for 3 hours after dropping, add water to quench the reaction, then separate the layers, dry the organic layer with anhydrous magnesium sulfate, and filter After vacuum distillation, 1.43 g of 1,4-diphenylbutane was obtained with a yield of 68%. 1 HNMR (400 MHz, CDCl 3 ) δ =1.65-1.73 (m, 4H), 2.61-2.68(m, 4H),7.14-7.22 (m, 6H),7.25-7.32 (m, 4H).

example 3

[0017] Example 3 Synthesis of 1,5-diphenylpentane

[0018] Under argon protection, 5 mL of toluene was added to the dry reaction vessel at 10 °C, then 8 mL of n-butyllithium (2.5 M n-hexane solution) was added dropwise with stirring, and 5 mL of tetrahydrofuran was slowly added dropwise at the end of the addition. After reacting at 10 ºC for 5 hours, add 1.13 g of 1,3-dichloropropane dropwise to the reaction system, and react for 3 hours after dropping, add water to quench the reaction, then separate the layers, dry the organic layer with anhydrous magnesium sulfate, and filter Distilled under reduced pressure to obtain 2.0 g of 1,5-diphenylpentane with a yield of 89%. 1 HNMR (400 MHz, CDCl 3 ) δ = 1.96-2.06 (m, 2H), 2.66-2.74 (m, 4H), 7.19-7.25 (m, 6H),7.27-7.35 (m, 4H).

technical field

[0001] The invention relates to a synthesis method of a class of organic compounds, in particular to a synthesis method of diphenylalkane, and belongs to the field of organic synthesis. Background technique

[0002] As a class of important intermediates, diphenylalkane compounds play an important role in the field of fluorescent probes. In addition, they can also be used as precursors for the synthesis of calixarenes and initiators for polymerization reactions. Diphenylalkane compounds also have a significant effect in improving the viscosity index of lubricating oils.

[0003] At present, the synthesis methods of diphenylalkane compounds mainly include: (1) the coupling of aryl Grignard reagent and dihaloalkane under metal complex catalysis to obtain diphenylalkane compound (Chem. Eur. J. 2009, 15, 3889; Chem. Commun. 2006, 4726; Tetrahedron 2006, 62, 2207); (2) Aromatics and ClO(CH 2 ) n COCl undergoes Friedel-Crafts reaction under the action of aluminum...

Examples

example 1

[0013] Example 1 Synthesis of 1,3-diphenylpropane

[0014] Under argon protection, 10 mL of toluene was added to the dry reaction vessel at 20 °C, then 8 mL of n-butyllithium (2.5 M n-hexane solution) was added dropwise with stirring, and 10 mL of tetrahydrofuran was slowly added dropwise at the end of the addition. After reacting at 20 ºC for 3 hours, add 0.85 g of dichloromethane dropwise to the reaction system, and react for 3 hours after dropping, add water to quench the reaction, then separate the layers, dry the organic layer with anhydrous magnesium sulfate, filter and distill under reduced pressure to obtain 1,3-diphenylpropane 1.24g, yield 63%. 1 HNMR (400MHz, CDCl 3 ) δ = 1.96-2.06 (m, 2H), 2.66-2.74 (m, 4H), 7.19-7.25 (m, 6H), 7.27-7.35 (m, 4H).

example 2

[0015] Example 2 Synthesis of 1,4-diphenylbutane

[0016] Under argon protection, 10 mL of toluene was added to the dry reaction vessel at 20 °C, then 8 mL of n-butyllithium (2.5 M n-hexane solution) was added dropwise with stirring, and 10 mL of tetrahydrofuran was slowly added dropwise at the end of the addition. After reacting at 20 ºC for 3 hours, add 1.0 g of 1,2-dichloroethane dropwise to the reaction system, and react for 3 hours after dropping, add water to quench the reaction, then separate the layers, dry the organic layer with anhydrous magnesium sulfate, and filter After vacuum distillation, 1.43 g of 1,4-diphenylbutane was obtained with a yield of 68%. 1 HNMR (400 MHz, CDCl 3 ) δ =1.65-1.73 (m, 4H), 2.61-2.68(m, 4H),7.14-7.22 (m, 6H),7.25-7.32 (m, 4H).

example 3

[0017] Example 3 Synthesis of 1,5-diphenylpentane

[0018] Under argon protection, 5 mL of toluene was added to the dry reaction vessel at 10 °C, then 8 mL of n-butyllithium (2.5 M n-hexane solution) was added dropwise with stirring, and 5 mL of tetrahydrofuran was slowly added dropwise at the end of the addition. After reacting at 10 ºC for 5 hours, add 1.13 g of 1,3-dichloropropane dropwise to the reaction system, and react for 3 hours after dropping, add water to quench the reaction, then separate the layers, dry the organic layer with anhydrous magnesium sulfate, and filter Distilled under reduced pressure to obtain 2.0 g of 1,5-diphenylpentane with a yield of 89%. 1 HNMR (400 MHz, CDCl 3 ) δ = 1.96-2.06 (m, 2H), 2.66-2.74 (m, 4H), 7.19-7.25 (m, 6H),7.27-7.35 (m, 4H).

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